US20060188739A1 - Composite formed article comprising vulcanizing rubber and thermoplastic elastomer and use thereof - Google Patents

Composite formed article comprising vulcanizing rubber and thermoplastic elastomer and use thereof Download PDF

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US20060188739A1
US20060188739A1 US10/548,870 US54887005A US2006188739A1 US 20060188739 A1 US20060188739 A1 US 20060188739A1 US 54887005 A US54887005 A US 54887005A US 2006188739 A1 US2006188739 A1 US 2006188739A1
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rubber
thermoplastic elastomer
molded product
ethylene
vulcanized rubber
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Tadashi Imai
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/121—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/84—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks by moulding material on preformed parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/84—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks by moulding material on preformed parts to be joined
    • B29C70/845—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks by moulding material on preformed parts to be joined by moulding material on a relative small portion of the preformed parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J10/00—Sealing arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J10/00—Sealing arrangements
    • B60J10/15—Sealing arrangements characterised by the material
    • B60J10/16—Sealing arrangements characterised by the material consisting of two or more plastic materials having different physical or chemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J10/00—Sealing arrangements
    • B60J10/20—Sealing arrangements characterised by the shape
    • B60J10/21—Sealing arrangements characterised by the shape having corner parts or bends
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J10/00—Sealing arrangements
    • B60J10/20—Sealing arrangements characterised by the shape
    • B60J10/23—Sealing arrangements characterised by the shape assembled from two or more parts
    • B60J10/233—Modular sealing arrangements, i.e. arrangements built up from a large number of joined modules
    • B60J10/2335—Modular sealing arrangements, i.e. arrangements built up from a large number of joined modules with joint end members, e.g. abutting ends
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14336—Coating a portion of the article, e.g. the edge of the article
    • B29C45/14409—Coating profiles or strips by injecting end or corner or intermediate parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/06—Sealing strips
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer

Definitions

  • the present invention relates to a composite molded product (also referred to as a molded composite) comprising thermoplastic elastomer melt-bonded to vulcanized rubber and use thereof and particularly to a composite molded product used as a corner profile joint or profile terminal part such as a weather strip, a door trim etc. in automobiles.
  • a composite molded product also referred to as a molded composite
  • thermoplastic elastomer melt-bonded to vulcanized rubber and use thereof and particularly to a composite molded product used as a corner profile joint or profile terminal part such as a weather strip, a door trim etc. in automobiles.
  • production of a weather strip having a joint is carried out generally by cutting an extruded vulcanized molded product consisting of a rubber blend of an ethylene/propylene/non-conjugated diene terpolymer (EPDM), setting the cut product in one or both sides of a mold, injecting a rubber molding material of the same type as that of the rubber blend of EPDM into the formed cavity, and vulcanizing and molding it.
  • EPDM ethylene/propylene/non-conjugated diene terpolymer
  • thermoplastic elastomer composition not requiring the step of vulcanization is commenced to be used as the material to be molded with a mold in place of vulcanized rubber using an ethylene/propylene/non-conjugated diene terpolymer (EPDM).
  • EPDM ethylene/propylene/non-conjugated diene terpolymer
  • the vulcanized rubber and the thermoplastic elastomer cannot be bonded to each other by vulcanization etc., and are thus formed into one piece via an adhesive, but this cannot be said to be satisfactory in respect of productivity or environmental compatibility.
  • thermoplastic elastomer As techniques of improving adhesiveness by devising the formulation of thermoplastic elastomer, there are those involving addition of polar group-containing resin to thermoplastic elastomer (for example, Japanese Patent Application Laid-Open No.2-115249, Japanese Patent Application Laid-Open No. 8-244068, Japanese Patent Application Laid-Open No. 10-324200).
  • thermoplastic elastomer for example, Japanese Patent Application Laid-Open No. 9-40814.
  • thermoplastic elastomer and vulcanized rubber there are not only techniques concerning the formulations of thermoplastic elastomer and vulcanized rubber described above, but also an art that involves cutting vulcanized rubber and then embossing the cut surface to achieve an anchor effect (see, for example, Japanese Patent Application Laid-Open No. 9-118133) and an art that involves applying polyolefin resin powder onto a cut surface of vulcanized rubber (see, for example, Japanese Patent Application Laid-Open No. 6-47816).
  • the present invention relates to a vulcanized rubber molded product and use thereof, and particularly to a vulcanized rubber molded product preferable for fusing molding of thermoplastic elastomer used as a corner profile joint or profile terminal part such as a weather strip and a door trim in an automobile.
  • the object of the present invention is to provide a vulcanized rubber molded product which upon melt bonding of thermoplastic elastomer without an adhesive layer, can form a molded product having sufficient adhesion while generating matrix breakage upon release, as well as a molded composite comprising thermoplastic elastomer melt-bonded to the vulcanized rubber molded product.
  • the vulcanized rubber molded product of the present invention is a vulcanized rubber molded product which is used for melt-bonding to olefinic thermoplastic elastomer and contains 2 to 10 wt % olefinic resin having a crystallinity of 10% or more as determined by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the molded composite of the present invention is a molded composite comprising (1) a vulcanized rubber molded product containing 2 to 10 wt % olefinic resin having a crystallinity of 10% or more as determined by a differential scanning calorimeter (DSC) joined to (2) a molded product consisting of a thermoplastic elastomer containing 10 wt % or more olefinic resin having a crystallinity of 10% or more as determined by a differential scanning calorimeter (DSC) and having a gel fraction of 30 wt % or less.
  • the molded composite is used preferably in an interior or exterior decorative material for an automobile, particularly in a weather strip.
  • FIG. 1 (A) is a schematic perspective view showing one example of a weather strip for an automobile, wherein the linear part is formed from a vulcanized rubber molded product, and the corner part is formed from a thermoplastic elastomer composition
  • FIG. 1 (B) is a schematic perspective view showing a method of forming the corner part of the weather strip.
  • the vulcanized rubber molded product according to the present invention comprises 2 to 10 wt % olefinic resin.
  • vulcanized in the present invention refers to formation of a crosslinked molecular reticulated structure as defined in “Kobunshi Daijiten” (Enlarged Polymer Dictionary), published in 1994 by Maruzen Co., Ltd., and the vulcanized rubber is completely crosslinked rubber.
  • the olefinic resin incorporated into the vulcanized rubber is an olefinic resin having a crystallinity of 10% or more as determined by a differential scanning calorimeter (DSC), and such olefinic resin includes C2 to C20, preferably C2 to C10, ⁇ -olefin homopolymers or copolymers.
  • DSC differential scanning calorimeter
  • C2 to C20 ⁇ -olefin examples include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-l-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-l-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-l-hexene, 3-ethyl-1-hexene, 9-methyl-1-pen
  • the melt flow rate (MFR; ASTM D 1238, 190° C., loading 2.16 kg) of the olefinic resin is preferably 0.01 to 500 g/10 min., more preferably 0.1 to 100 g/10 min.
  • the [ ⁇ ] (intrinsicviscosity measured in decalin at 135° C.) of the olefinic resin is 0.1 to 10 dl/g, preferably 0.5 to 5 dl/g.
  • the olefinic resin examples include polyethylene, polypropylene, polybutene etc., and particularly, low-density polyethylene, linear low-density polyethylene and polypropylene are preferable.
  • the density (ASTM D 1505) of the low-density polyethylene and linear low-density polyethylene in the present invention is 0.870 to 0.94 g/cm 3 , preferably 0.875 to 0.935 g/cm 3 , more preferably 0.880 to 0.930 g/cm 3 .
  • the low-density polyethylene and linear low-density polyethylene in the present invention have at least one endothermic peak (Tm) at 80 to 140° C., preferably 90 to 130° C., more preferably 100 to 130° C., in measurement with DSC.
  • Tm endothermic peak
  • the endothermic peak was determined from an endothermic curve prepared by packaging an aluminum pan with a sample, heating it to 200° C. at a rate of 100° C./min., keeping it at 200° C. for 10 minutes, then cooling it to ⁇ 150° C. at a rate of 100° C./min., and heating it at a rate of 10° C./min.
  • Each of the low-density polyethylene and linear low-density polyethylene is an ethylene homopolymer or a crystalline ethylene/ ⁇ -olefinic copolymer consisting of ethylene and C3 to C20, preferably C3 to C8, ⁇ -olefin.
  • the polyethylene contains a comonomer, the content of the comonomer is as low as 25% or less based on the total.
  • the low-density polyethylene and linear low-density polyethylene used in the present invention are usually those having a crystallinity of 10% or more as determined by a differential scanning calorimeter (DSC).
  • the polyethylene includes an ethylene/butene-1 copolymer, an ethylene/propylene copolymer, an ethylene/hexane copolymer, an ethylene/octene copolymer etc., and is preferably at least one member selected from low-density polyethylene and linear low-density polyethylene.
  • the polyethylene may be a blend of two or more of these copolymers or may consist of both high-density polyethylene and low-density polyethylene.
  • the polymer may consist of two or more kinds of low-density polyethylene and two or more kinds of linear low-density polyethylene.
  • a catalyst etc. used in production of the crystalline ethylene-based polymer are not particularly limited, the polymer is produced by a general Ziegler-Natta catalyst, a metallocene catalyst or the like.
  • the melt flow rate (MFR; ASTM D 1238, 190° C., loading 2.16 kg) of the low-density polyethylene and linear low-density polyethylene used in the present invention is preferably 0.01 to 500 g/10 min. or less, more preferably 0.1 to 100 g/10 min., still more desirably 0.5 to 50 g/10 min.
  • the polypropylene used in the present invention includes a propylene homopolymer and a propylene copolymer produced by random copolymerization or block copolymerization of propylene with ethylene and/or C4 to C20 ⁇ -olefin.
  • the C4 to C20 ⁇ -olefin includes the above-mentioned ⁇ -olefins.
  • the comonomer to be copolymerized with propylene is preferably ethylene or 1-butene.
  • the content of a constituent unit (propylene content) derived from propylene in this propylene copolymer is usually 50 to 90% by weight, and the content of a constituent unit (comonomer content) derived from the comonomer is usually 50 to 10% by weight.
  • the formulation of the propylene copolymer is determined by 13 C-NMR.
  • the melt flow rate (MFR; ASTM D 1238, 230° C., loading 2.16 kg) of the polypropylene is usually 0.01 to 100 g/10 min., preferably 0.1 to 80 g/10 min., more preferably 0.3 to 60 g/10 min.
  • the melting point (Tm) of the polypropylene, as determined by DSC, is usually 170° C. or less.
  • the content of the olefinic resin in the vulcanized rubber molded product is 2 to 10% by weight.
  • the content is preferably 3 to 8% by weight, more preferably 4 to 5% by weight, based on the total weight (assumed to be 100% by weight) of the vulcanized rubber molded product.
  • the vulcanized rubber molded product according to the present invention is preferably based on an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer rubber.
  • the ⁇ -olefin in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer rubber is preferably a C3 to C20 ⁇ -olefin, and specific examples include the above-mentioned ⁇ -olefins.
  • C3 to C8 ⁇ -olefins for example propylene, 1-butene, 4-methylpentene-1,1-hexene and 1-octene are particularly preferable.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer rubber comprises (a) a unit derived from ethylene and (b) a unit derived from a C3 to C20 ⁇ -olefin, in a molar ratio of 50/50 to 90/10 [(a)/(b)] in order to give a rubber composition capable of providing a vulcanized rubber molded product excellent in resistance to heating and aging, strength properties, rubber elasticity, resistance to cold, and processability.
  • This molar ratio is more preferably 65/35 to 90/10, still more preferably 65/35 to 85/15, further more preferably 65/35 to 80/20.
  • non-conjugated polyene examples include:
  • linear non-conjugated dienes such as 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene etc.;
  • cyclic non-conjugated dienes such as methyl tetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene etc.; and
  • trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene etc.
  • non-conjugated polyenes 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene, and 4-ethylidene-8-methyl-1,7-nanodiene are particularly preferable.
  • non-conjugated polyenes can be used alone or as a mixture of two or more thereof.
  • the iodine value of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer is preferably 1 to 40, more preferably 1 to 30, in respect of an advantage in cost and in order to give a rubber composition of high crosslinking efficiency to provide a vulcanized rubber molded product excellent in resistance to compressive permanent distortion.
  • the Mooney viscosity [ML1+4 (125° C.)] of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer rubber is preferably 10 to 250, more preferably 40 to 150, in order to give a rubber composition capable of providing a vulcanized rubber molded product excellent in processability, strength properties and resistance to compressive permanent distortion.
  • These ethylene/ ⁇ -olefin/non-conjugated polyene copolymer rubbers may be used alone or as a mixture of two or more thereof.
  • carbon black is used preferably in an amount of 30 to 300 parts by weight based on 100 parts by weight of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer rubber in order to give an extrusion-molded vulcanized rubber molded product having sufficient mechanical strength.
  • carbon black As the carbon black, it is possible to.use carbon black such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT etc.
  • the nitrogen adsorption specific surface area of carbon black is preferably 10 to 100 m 2 /g in order to give a rubber composition capable of providing a vulcanized rubber molded product excellent in mechanical strength and product skin.
  • additives such as an antioxidant, a processing aid, a foaming agent, a foaming aid, a coloring agent, a dispersant and a flame retardant are added to the vulcanized rubber.
  • inorganic fillers can be used suitably as a reinforcing material in the vulcanized rubber, and the amount of the inorganic fillers is usually up to 100 parts by weight based on 100 parts by weight of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer rubber.
  • the inorganic fillers include silica, light calcium carbonate, heavy calcium carbonate, talc, clay etc.
  • a softening agent used usually in rubber can be used. Specific examples include:
  • petroleum-based softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, vaseline, etc.;
  • coal tar-based softening agents such as coal tar, coal tar pitch, etc.
  • fatty oil-based softening agents such as castor oil, linseed oil, grapeseed oil, soybean oil, coconut oil, etc.;
  • wax such as beeswax, carnauba wax, lanoline, etc.
  • fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, zinc laurate, etc.;
  • pine acid, rosin or its derivatives pine acid, rosin or its derivatives
  • ester-based softeners such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate, etc.;
  • microcrystalline wax liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal-modified polyisoprene, hydrogenated terminal-modified polyisoprene, liquid Thiokol, hydrocarbon-based synthetic lubricating oil, etc.
  • petroleum softeners particularly process oil, are preferably used. The amount of these softeners incorporated is selected suitably depending on applications of the vulcanized product.
  • the vulcanizing agent used in production of the vulcanized rubber includes sulfur and sulfur compounds.
  • the vulcanized rubber includes not only rubber crosslinked with sulfur but also rubber crosslinked with another crosslinking agent.
  • the sulfur includes powder sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur etc.
  • the sulfur compounds include sulfur chloride, sulfur dichloride, high-molecular polysulfide, etc.
  • Use can also be made of sulfur compounds releasing active sulfur at their vulcanization temperature, for example morpholine disulfide, alkyl phenol disulfide, tetramethyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, selenium dimethyl dithiocarbamate, etc.
  • sulfur is preferable.
  • Sulfur or the sulfur compound is used usually in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the copolymer rubber.
  • a vulcanization accelerator is preferably simultaneously used.
  • Specific examples of the vulcanization accelerator include:
  • Sulfonamide-based compounds such as N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-oxydiethylene-2-benzothiazole sulfenamide (OBS), N-t-butyl-2-benzothiazole sulfenamide (BBS), N,N-diisopropyl-2-benzothiazole sulfenamide, etc.;
  • CBS N-cyclohexyl-2-benzothiazole sulfenamide
  • OBS N-oxydiethylene-2-benzothiazole sulfenamide
  • BBS N-t-butyl-2-benzothiazole sulfenamide
  • N,N-diisopropyl-2-benzothiazole sulfenamide etc.
  • thiazole-based compounds such as 2-mercaptobenzothiazole (MBT), 2-(2,4-dinitrophenyl) mercaptobenzothiazole, 2-(4-morpholinothio) benzothiazole, 2-(2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl disulfide, etc.;
  • guanidine-based compounds such as diphenyl guanidine (DPG), triphenyl guanidine, diorthonitrile guanidine (DOTG), orthotollyl biguanide, diphenyl guanidine naphthalate, etc.;
  • aldehyde amine or aldehyde/ammonia-based compounds such as an acetaldehyde/aniline condensate, a butyl aldehyde/aniline condensate, hexamethylene tetramine (H), acetaldehyde ammonia, etc.;
  • imidazoline-based compounds such as 2-mercaptoimidazoline etc.
  • thiourea-based compounds such as thiocarbanilide, diethyl thiourea (EUR), dibutyl thiourea, trimethyl thiourea, diorthotollyl thiourea, etc.;
  • thiuram-based compounds such as tetramethyl thiuram sulfide (TMTM), tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, tetrakis(2-ethylhexyl) thiuram disulfide (TOT), dipentamethylene thiuram tetrasulfide (TRA), etc.;
  • TMTM tetramethyl thiuram sulfide
  • TMTD tetramethyl thiuram disulfide
  • TOT tetrabutyl thiuram disulfide
  • TOT tetrakis(2-ethylhexyl) thiuram disulfide
  • TRA dipentamethylene thiuram tetrasulfide
  • dithiocarbamates such as zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc di-n-butyl dithiocarbamate, zinc ethylphenyl dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyl dithiocarbamate, selenium dimethyl dithiocarbamate, tellurium dimethyl dithiocarbamate, etc.;
  • xanthogenates such as zinc dibutyl xanthogenate etc.
  • vulcanization accelerators are used usually in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the copolymer rubber.
  • the antioxidant used in the vulcanized rubber includes an amine-based antioxidant, a hindered phenol-based inhibitor and a sulfur-based inhibitor, and these antioxidants are used in such a range that the object of the present invention is not hindered.
  • the amine-based antioxidant includes diphenyl amines, phenylene diamines, etc.
  • sulfur-based antioxidant a sulfur-based antioxidant used usually in rubber is used.
  • a processing aid used usually in rubber is used.
  • Specific examples include higher fatty acids such as linoleic acid, ricinoleic acid, stearic acid, palmitic acid, lauric acid etc., higher fatty acid salts such as barium stearate, zinc stearate, calcium stearate, etc., and esters of these higher fatty acids.
  • processing aids are used usually in an amount of 10 parts by weight or less based on 100 parts by weight of the ethylene/ ⁇ -olefin/non-conjugatedpolyene copolymer rubber, but desirably the optimum amount is determined depending on required physical values.
  • the foaming agent include inorganic foaming agents such as sodium bicarbonate (baking soda), sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, etc.; nitroso compounds such as N,N′-dimethyl-N,N′-dinitrosoterephthalamide, N,N′-dinitrosopentamethylene tetramine (DPT), etc.; azo compounds such as azodicarbonamide (ADCA), azobisisobutyronitrile (AZBN), azobiscyclohexyl nitrile, azodiaminobenzene, barium azodicarboxylate, etc.; sulfonyl hydrazide compounds such as benzene sulfonyl hydrazide (BSH), toluene sulfonyl hydrazide (TSH), p,p′-oxybis (benzene sulfonyl hydrazide) (
  • the other rubber can also be used by blending it with the components of the vulcanized rubber.
  • the other rubber includes natural rubber (NR), isoprene-based rubber such as isoprene rubber (IR) etc., and conjugated diene-based rubber such as butadiene rubber (BR), styrene/butadiene rubber (SBR), acrylonitrile/butadiene rubber (NBR), chloroprene rubber (CR) etc.
  • natural rubber NR
  • isoprene-based rubber such as isoprene rubber (IR) etc.
  • conjugated diene-based rubber such as butadiene rubber (BR), styrene/butadiene rubber (SBR), acrylonitrile/butadiene rubber (NBR), chloroprene rubber (CR) etc.
  • the rubber composition used in preparation of the vulcanized rubber molded product can be prepared by kneading ethylene/ ⁇ -olefin/non-conjugated polyene copolymer rubber, carbon black, a rubber-reinforcing agent, an inorganic filler and additives such as a softening agent at a temperature of 80 to 170° C.
  • an internal mixer such as a Banbury mixer, a kneader or an intermix
  • a vulcanizing agent such as sulfur and if necessary a vulcanization accelerator, a vulcanization aid, a foaming agent and a foaming aid
  • a roll such as an open roll or a kneader, kneading the mixture at a roll temperature of 40 to 80° C. for 5 to 30 minutes, and dispensing it.
  • the rubber composition for extrusion molding prepared in the manner described above, is formed into an intended shape by an extrusion molding machine, and simultaneously with this molding or after introduction of the molded product into a vulcanization bath, is vulcanized by heating at a temperature of 140 to 300° C. for 1 to 20 minutes.
  • the vulcanization process is conducted continuously.
  • a heating means such as hot air, a glass beads fluidized bed, liquid curing medium, (LCM), PCM (powder curing medium or powder curing method), UHF (ultra high frequency) or steam can be used.
  • the vulcanized rubber molded product of the present invention has been gelled, and cannot be measured for fluidity (for example MFR) even after milling of the molded product.
  • thermoplastic elastomer refers to a thermoplastic elastomer consisting of olefinic resin and olefinic rubber.
  • thermoplastic elastomer has physical properties similar to those of rubber, for example flexibility and impact resilience, and can be processed as thermoplastics in contrast to conventional rubber, and such explanation appears in, for example, “Kobunshi Daijiten” (Enlarged Polymer Dictionary), published in 1994 by Maruzen Co., Ltd.
  • the content of the olefinic resin in the thermoplastic elastomer according to the present invention is higher than 10% by weight, and is preferably 15 to 70% by weight, more preferably 20 to 60% by weight.
  • the thermoplastic elastomer used in the present invention is a thermoplastic elastomer forming a morphology of islands-sea structure wherein the average particle diameter of the island phase is 2 ⁇ m or less.
  • the island phase is composed mainly of a crosslinked (gelled) component.
  • the island s-sea structure refers to a phase structure having dispersed particles in matrix.
  • the average particle diameter of the island phase can be determined by measuring a sample sampled arbitrarily from a photograph magnified 10,000-times under a transmission electron microscope.
  • the average particle diameter of the island phase was expressed specifically in terms of the average of the minor axis and major axis (that is, the average of (minor axis+major axis)/2) of every island phase in an electron microphotograph.
  • the gel fraction of the thermoplastic elastomer of the present invention is 30% by weight or less.
  • the gel fraction of the thermoplastic elastomer according to the present invention is preferably 20% by weight or less, more preferably 10% by weight or less.
  • the lower limit is not particularly limited and may be 0% by weight, that is, no crosslinked product may be contained.
  • the method of measuring the gel fraction is as follows.
  • thermoplastic elastomer pellets were weighed out as a sample, wrapped with a 325-mesh screen, and dipped at 140° C. for 24 hours in p-xylene in an amount (30 ml) enough for the pellets in a closed container.
  • the content of the non-crosslinked ethylene-based component (ethylene-based resin -or ethylene-based rubber) in the thermoplastic elastomer according to the present invention is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, still more preferably 15 to 30% by weight.
  • the content of the non-crosslinked ethylene-based component (ethylene-based resin, ethylene-based rubber) can be determined from gel fraction.
  • the sea phase is a non-crosslinked component and the island phase is a crosslinked component in many cases.
  • the ethylene-based resin component includes high-density, polyethylene, low-density polyethylene, linear low-density polyethylene etc.
  • ethylene-based rubber component ethylene/propylene rubber, ethylene/butene-1 copolymer rubber, ethylene/hexene-1 copolymer rubber, ethylene/octene-1 copolymer rubber and ethylene/propylene/butene-1 copolymer rubber are particularly preferable.
  • thermoplastic elastomer is melt-bonded to the vulcanized rubber molded product described above, breakage of the matrix easily occurs upon release by pulling.
  • the olefinic thermoplastic elastomer of the present invention is obtained by dynamic heat-treatment of a blend consisting of olefinic resin and olefinic rubber in the presence or absence of a crosslinking agent.
  • the olefinic thermoplastic elastomer of the present invention may also be obtained by dynamically heat-treating a blend consisting of olefinic resin and olefinic rubber in the presence or absence of a crosslinking agent, then adding non-crosslinked olefinic resin and/or an olefinic rubber component (preferably the above-mentioned ethylene-based component) to the resulting thermoplastic elastomer, and then dynamically heat-treating the mixture.
  • the ratio of the olefinic resin to the olefinic rubber compounded as the starting material can be determined suitably such that the content of the olefinic resin in the finally obtained olefinic thermoplastic elastomer composition is higher than 10% by weight.
  • the amount of the olefinic resin having a crystallinity of 10% or more as determined by a differential scanning calorimeter (DSC) is determined by a differential scanning calorimeter (DSC) from the weight of a polymer obtained by extracting the thermoplastic elastomer in boiling xylylenel and precipitating its soluble fraction in methyl ethyl ketone.
  • the amount of the crosslinking agent used and the amount of the non-crosslinked olefinic resin and/or olefinic rubber component added after crosslinkage can be regulated to achieve the desired gel fraction and the content of the non-crosslinked ethylene-based component.
  • the olefinic resin serving as a starting material of the thermoplastic elastomer of the present invention has a crystallinity of 10% or more as determined by a differential scanning calorimeter (DSC).
  • the melt flow rate (MFR; ASTM D 1238, 190° C., loading 2.16 kg) of the olefinic resin is preferably 0.01 to 500 g/10 min., more preferably 0.1 to 100 g/10 min.
  • the olefinic resin of the present invention includes a C2 to C20, preferably C2 to C10, ⁇ -olefin homopolymer or copolymer.
  • the ⁇ -olefin includes the same ⁇ -olefins as described above.
  • the olefinic resin includes polyethylene, polypropylene, polybutene etc., among which low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and polypropylene are particularly preferable.
  • low-density polyethylene linear low-density polyethylene and polypropylene
  • the same low-density polyethylene, linear low-density polyethylene and polypropylene as described above in the item of the olefinic resin added to the vulcanized rubber can be used.
  • the density (ASTM D 1505) of the high-density polyethylene is higher than 0.94 g/cm 3 , and is preferably 0.945 to 0.980 g/cm 3 , more preferably 0.950 to 0975 g/cm 3 .
  • This high-density polyethylene is an ethylene homopolymer or a crystalline ethylene/ ⁇ -olefinic copolymer consisting of ethylene and a C3 to C20, preferably C3 to C8, ⁇ -olefin.
  • a comonomer When a comonomer is contained, the content of the comonomer is as small as 25 mol % or less based on the total.
  • Specific examples include an ethylene/butene-1 copolymer, an ethylene/propylene copolymer, an ethylene/octene copolymer, etc.
  • the olefinic rubber serving as a starting material of the thermoplastic elastomer of the present invention has a crystallinity of less than 10% as determined by a differential scanning calorimeter (DSC).
  • the olefinic rubber in the present invention is an amorphous random elastic copolymer containing at least 50 mol % C2 to C20 ⁇ -olefin, and examples thereof include a non-crystalline ⁇ -olefin copolymer consisting of 2 or more kinds of ⁇ -olefins and an ⁇ -olefin/non-conjugated diene copolymer consisting of 2 or more kinds of ⁇ -olefins and non-conjugated dienes.
  • olefinic copolymer rubber examples include the following rubber:
  • ⁇ -olefin examples include the ⁇ -olefins described above.
  • non-conjugated diene examples include the above-described non-conjugated dienes, among which dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene are preferable.
  • the Mooney viscosity [ML1+4 (100° C.)] of the copolymer rubber is preferably 10 to 250, particularly 40 to 150.
  • the iodine value of the ethylene/( ⁇ -olefin/non-conjugated diene copolymer rubber (2) is preferably 25 or less.
  • ethylene/propylene/non-conjugated diene rubber is particularly preferably used.
  • the rubber used in the present invention includes not only the above-mentioned olefinic copolymer rubber but also rubber other than the olefinic copolymer rubber, for example diene-based rubber such as styrene/butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR) and butyl rubber (IIR), SEBS, polyisobutylene, etc.
  • diene-based rubber such as styrene/butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR) and butyl rubber (IIR), SEBS, polyisobutylene, etc.
  • the crosslinking agent used in the present invention includes, for example, organic peroxides, sulfur, sulfur compounds, and phenol-based vulcanizing agents such as phenol resin, among which the organic peroxides are preferably used.
  • organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexyne-3,1,3-bis(tert-butylperoxy isopropyl) benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethyl cyclohexane, n-butyl-4,4-bis(tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, la
  • 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexyne-3, 1,3-bis(tert-butylperoxyisopropyl) benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and n-butyl-4,4-bis(tert-butylperoxy) valerate are preferable in respect of smell and scorch stability, among which 1,3-bis (tert-butylperoxyisopropyl) benzene ismost preferable.
  • This organic peroxide is used in an amount of 0.01 to 0.4 part by weight, preferably about 0.03 to 0.3 part by weight, based on 100 parts by weight of the olefinic resin and olefinic rubber in total.
  • crosslinking treatment with the organic peroxide in the present invention it is possible to incorporate a crosslinking aid such as sulfur, p-quinone dioxime, p,p′-dibenzoyl quinonedioxime, N-methyl-N,4-dinitrosoaniline, nitrobenzene, diphenyl guanidine or trimethylol propane-N,N′-m-phenylene dimaleimide, divinyl benzene, triallyl cyanurate, a multifunctional methacrylate monomer such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol propane trimethacrylate or allyl methacrylate, or a multifunctional vinyl monomer such as vinyl butyrate or vinyl stearate.
  • a crosslinking aid such as sulfur, p-quinone dioxime, p,p′-dibenzoyl quinonedioxime, N-methyl-
  • divinyl benzene is most preferable because it is easily handled, is excellent in compatibility with the olefinic resin or olefinic rubber as the material to be treated, and has an action of solubilizing organic peroxides to act as a dispersing agent for the organic peroxides, thus attaining a uniform crosslinking effect by heat treatment to give a, composition having good balance between fluidity and physical properties.
  • the amount of such crosslinking aids or multifunctional vinyl monomers incorporated is usually in the range of 0.01 to 0.4 wt %, particularly 0.03 to 0.3 wt %, based on 100 parts by weight of the olefinic resin and olefinic rubber in total.
  • Additives such as a softening agent, a slip agent, a filler, an antioxidant, a weathering stabilizer and a coloring agent can be incorporated into the olefinic thermoplastic elastomer according to the present invention if necessary in such a range that the object of the present invention is not hindered.
  • dynamic heat-treating refers to kneading in a molten state (this applies hereinafter).
  • the dynamic heat-treatment in the present invention is conducted preferably in an apparatus in a closed system, and conducted preferably in an atmosphere of an inert gas such as nitrogen, carbon dioxide gas, etc.
  • the kneading temperature is usually 150 to 280° C., preferably 170 to 240° C.
  • the kneading time is usually 1 to 20 minutes, preferably 3 to 10 minutes.
  • Applied shear force, in terms of shear rate, is 10 to 100,000 sec ⁇ 1 , preferably 100 to 50,000 sect ⁇ 1 .
  • a mixing roll an intensive mixer (for example a Banbury mixer, a kneader) or a single- or twin-screw extruder is used, and the apparatus is preferably in a closed system.
  • an intensive mixer for example a Banbury mixer, a kneader
  • a single- or twin-screw extruder is used, and the apparatus is preferably in a closed system.
  • the melt flow rate (MFR; ASTM D 1238, 230° C., loading 2.16 kg) of the thus obtained olefinic thermoplastic elastomer according to the present invention is usually 0.01 to 1000 g/10 min., preferably 0.05 to 500 g/10 min., more preferably 0.1 to 100 g/10 min.
  • the thermoplastic elastomer having a melt flow rate in the above range is excellent in moldability.
  • the molded composite according to the present invention comprises an olefinic thermoplastic elastomer joined to, preferably melt-bonded to, the vulcanized rubber molded product.
  • the adhesion of a joint of the molded composite according to the present invention in terms of peel strength in a peel strength test described later, is 40 MPa or more, preferably 45 MPa or more, and interfacial release is hardly observed, and the degree of breakage of the matrix is 80% or more, preferably 90% or more.
  • the composite molded product consisting of the vulcanized rubber molded product and thermoplastic elastomer according to the present invention is used preferably in an interior or exterior decorative material for an automobile, particularly preferably in a weather strip for an automobile.
  • the vulcanized rubber molded product according to the present invention is not limited to a weather strip, and can be used in other applications requiring adhesion to thermoplastic elastomer.
  • the weather strip material means a sealing material for an automobile, and includes a door weather strip, a bonnet weather strip, a glass run channel, etc.
  • a weather strip in molding of a corner wherein the extruded molded product of vulcanized rubber is cut and the resulting cut extruded molded products are connected to each other in different directions, a weather strip can be obtained by injection-molding the olefinic thermoplastic elastomer at a temperature of not lower than its melting point and then melt-bonding the injection-molded elastomer, by contacting, to the extruded molded products of vulcanized rubber.
  • the weather strip having a corner molded product consisting of the vulcanized rubber molded product and olefinic thermoplastic elastomer according to the present invention is described more specifically by reference to FIG. 1 .
  • FIG. 1 is a schematic perspective view showing a weather strip (glass run channel) for an automobile and a method of forming the same.
  • the weather strip is composed of cut extruded molded products 1 and 2 made of vulcanized rubber and a connecting corner member 3 formed upon connecting the cut extruded molded products 1 and 2 to each other in different directions.
  • the cut extruded molded products 1 and 2 are those obtained by injection-molding the vulcanized rubber in a channel form and then cut it in predetermined length.
  • the cut extruded molded products 1 and 2 have a linear shape in the longer direction.
  • the “connecting corner member” refers to the portion made of thermoplastic elastomer which is formed upon connecting the cut extruded molded products to each other in different directions.
  • the weather strip can be prepared in the following manner. First, a mold 4 for injection molding is previously heated to a predetermined temperature. As shown in FIG. 1 (B), the cut extruded molded products land 2 made of vulcanized rubber are then inserted into the mold 4 .
  • the olefinic thermoplastic elastomer molten at a temperature not lower than its melting point in a heating chamber is then injected into a space formed between the cavity of mold 4 and the core, and the olefinic thermoplastic elastomer molten at a temperature not lower than its melting point is melt-bonded to the edge faces of the cut extruded molded products 1 and 2 , followed by cooling the thermoplastic elastomer, to give the weather strip having a corner member 3 as shown in FIG. 1 (A).
  • Shore A hardness was measured in accordance with JIS K6301. Measurement conditions: A sheet was prepared by a pressing molding machine, and using an A-type measuring instrument, the scale was read just after a probe was contacted by pushing.
  • JIS K6301 a tensile test was conducted under the following conditions to determine tensile strength and elongation at breakage.
  • Test conditions A sheet was prepared by a pressing molding machine, and a test specimen JIS3 was punched out and examined under the condition of a stress rate of 200 mm/min.
  • the melt flow rate of the olefinic thermoplastic elastomer was measured at 230° C. under a loading of 2.16 kg in accordance with ASTM D 1238-65T.
  • the starting rubber was kneaded for 1 minute and then carbon black, calcium carbonate, the softening agent, stearic acid, zinc white No. 3, and the activating agent were added thereto and kneaded for 2 minutes. Thereafter, a ram was raised and cleaned, and the mixture was kneaded for additional 2 minutes to give 1670 g rubber blend (I). This kneading was conducted at a packing of 75%, and by the same operation, 3 batches were kneaded to give 5010 g blend in total.
  • the rubber blend (II) was vulcanized and molded by heating at 170° C. for 10 minutes with a 150-ton press to produce a flat plate of 12 cm in length, 14.7 cm in width and 2 mm in thickness.
  • a vulcanized press sheet (referred to hereinafter as vulcanized rubber molded product 1) was obtained in this manner.
  • HDPE-1 high-density polyethylene
  • a, phenol-based antioxidant [trade name: IRGANOX 1010, manufactured by Nihon Ciba-Geigy K.K.] as an antioxidant,
  • a diazo-based weathering stabilizer [trade name: Tinubine 326, manufactured by Nihon Ciba-Geigy K.K.] as a weathering stabilizer,
  • EPT-2 oil-extended ethylene/propylene/5-ethylidene-2-norbornene copolymer rubber
  • a phenol-based antioxidant [trade name: IRGANOX 1010, manufactured by Nihon Ciba-Geigy K.K.] as an antioxidant,
  • a diazo-based weathering stabilizer [tradename: Tinubine 326, manufactured by Nihon Ciba-Geigy K.K.] as a weathering stabilizer,
  • thermoplastic elastomer 1 The physical properties of the vulcanized rubber molded product 1 and thermoplastic elastomer 1 are shown in Table 1.
  • thermoplastic elastomer 1 was formed such that in the stage of injection molding, it was melt-bonded to, a cut section of the vulcanized rubber molded product 1 in a 100-ton injection molding machine. The resulting molded product was examined in the following tensile peel strength test.
  • the molded product comprising the molded product of vulcanized rubber joined to the molded product consisting of thermoplastic elastomer, that is, the weather strip in FIG. 1 , was examined in a tensile test by pulling it at a tensile rate of 200 mm/min. while holding two positions between which the connector was sandwiched, and after the test, whether the resulting section was due to matrix breakage or interfacial release was confirmed by observation, and the ratio of the thermoplastic elastomer remaining on the peel section to the adhesive surface was indicated as degree of breakage of matrix.
  • Table 1 The results are shown in Table 1.
  • a vulcanized rubber molded product 2 was obtained in the same manner as in Reference Example 1 except that EPT-3 below was used in place of EPT-1.
  • the same procedure as in Example 1 was conducted except that a vulcanized rubber molded product 2 was used in place of the vulcanized rubber molded product in Example 1.
  • the evaluation results are shown in Table 1.
  • a vulcanized rubber molded product 2 was obtained in the same manner as in Reference Example 1 except that a rubber composition (hereinafter referred to as EPT-3) containing 100 parts by weight of oil-extended ethylene/propylene/5-ethylidene-2-norbornene copolymer rubber (ethylene content, 68 mol %; propylene content, 32 mol %;. iodine value, 12; the amount of an oil extender, 10 parts by weight of paraffin-based process oil (trade name: PW-380, manufactured by Idemitsu Kosan.
  • EPT-3 oil-extended ethylene/propylene/5-ethylidene-2-norbornene copolymer rubber
  • ethylene content 68 mol %
  • propylene content 32 mol %
  • iodine value 12
  • the amount of an oil extender 10 parts by weight of paraffin-based process oil (trade name: PW-380, manufactured by Idemitsu Kosan.
  • An ethylene/propylene/5-ethylidene-2-norbornene copolymer rubber (ethylene content, 68 mol %; propylene content, 32 mol %; iodine value, 12; the amount of an oil extender, 10 parts by weight of paraffin-based process oil (tradename: PW-380, manufactured by Idemitsu Kosan Co., Ltd.) based on 100 parts by weight of the rubber; Mooney viscosity [ML 1+4 (125° C.)], 63) was used in place of EPT-1 in Reference Example 1, and FEF-grade carbon black [trade name: Asahi #60G, manufactured by Asahi Carbon Co., Ltd.] was used in an amount of 185 parts by weight, to give a vulcanized rubber molded product 3 .
  • the procedure was conducted in the same manner as in Example 1 except that the vulcanized rubber molded product 3 was used in place of the vulcanized rubber molded product 1 in Example 1.
  • the evaluation results are
  • Example 1 The procedure was carried out in the same manner as in Example 1 except that the thermoplastic elastomer 2 in Reference Example 3 was used in place of the thermoplastic elastomer 1 in Example 1. The evaluation results are shown in Table 1.

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US8399104B2 (en) * 2007-03-23 2013-03-19 Sumitomo Chemical Company, Limited Composite molded article and process for producing the same
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US11432536B2 (en) * 2020-09-11 2022-09-06 Central Gargen & Pet Company Aquarium conversion systems

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GB2417489B (en) 2007-04-04
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